Catalyst systems and their use in a polymerization process

ABSTRACT

The present invention relates to mixed catalyst system of a Group 15 containing metal catalyst compound, a bulky ligand metallocene-type catalyst compound, and a Lewis acid aluminum containing activator and to a supported version thereof and for their use in a process for polymerizing olefin(s).

RELATED APPLICATION DATA

[0001] The present application is a Divisional of U.S. patentapplication Ser. No. 09/460,179, filed on Dec. 10, 1999, now issued asU.S. Pat. No. ______.

FIELD OF THE INVENTION

[0002] The present invention relates to a catalyst system of Group 15containing transition metal catalyst compound, a bulky ligandmetallocene-type catalyst compound and a Lewis acid aluminum containingactivator catalysts and its use in the polymerization of olefin(s).

BACKGROUND OF THE INVENTION

[0003] Advances in polymerization and catalysis have resulted in thecapability to produce many new polymers having improved physical andchemical properties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization-type (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes. Especially illustrativeof these advances is the development of technology utilizing bulkyligand metallocene-type catalyst systems.

[0004] More recently, developments have lead to the discovery ofanionic, multidentate heteroatom ligands as discussed by the followingarticles: (1) Kempe et al., “Aminopyridinato Ligands—New Directions andLimitations”, 80^(th) Canadian Society for Chemistry Meeting, Windsor,Ontario, Canada, June 1-4, 1997; (2) Kempe et al., Inorg. Chem. 1996 vol35 6742; (3) Jordan et al. of polyolefin catalysts based onhydroxyquinolines (Bei, X.; Swenson, D. C.; Jordan, R. F.,Organometallics 1997, 16, 3282); (4) Horton, et.al., “CationicAlkylzirconium Complexes Based on a Tridentate Diamide Ligand: NewAlkene Polymerization Catalysts”, Organometallics, 1996, 15, 2672-2674relates to tridentate zirconium complexes; (5) Baumann, et al.,“Synthesis of Titanium and Zirconium Complexes that Contain theTridentate Diamido Ligand [((t—Bu—d₆)N—O—C₆H₄)₂O]²⁻{[NON}²⁻) and theLiving Polymerization of 1-Hexene by Activated [NON]ZrMe2”, Journal ofthe American Chemical Society, Vol. 119, pp. 3830-3831; (6) Cloke etal., “Zirconium Complexes incorporating the New Tridentate DiamideLigand [(Me₃Si)N{CH₂CH₂N(SiMe₃)}₂]²⁻ (L); the Crystal Structure of[Zr(BH₄)₂L] and [ZrCl{CH(SiMe₃)₂}L]”, J. Chem. Soc. Dalton Trans, pp.25-30, 1995; (7) Clark et al., “Titanium (IV) complexes incorporatingthe aminodiamide ligand [(SiMe₃)N{CH₂CH₂N (SiMe₃)}₂]²⁻(L); the X-raycrystal structure of [TiMe₂(L)] and [TiCl{CH(SiMe₃)₂}(L)]”, Journal ofOrganometallic Chemistry, Vol 50, pp. 333-340, 1995; (8) Scollard etal., “Living Polymerization of alpha-olefins by Chelating DiamideComplexes of Titanium”, J. Am. Chem. Soc., Vol 118, No. 41, pp.10008-10009, 1996; and (9) Guerin et al., “Conformationally RigidDiamide Complexes: Synthesis and Structure of Titanium (IV) AlkylDerivatives”, Organometallics, Vol 15, No. 24, pp. 5085-5089, 1996.

[0005] Furthermore, U.S. Pat. No. 5,576,460 describes a preparation ofarylamine ligands and U.S. Pat. No. 5,889,128 discloses a process forthe living polymerization of olefins using initiators having a metalatom and a ligand having two group 15 atoms and a group 16 atom or threegroup 15 atoms. EP 893 454 A1 also describes preferably titaniumtransition metal amide compounds. In addition, U.S. Pat. No. 5,318,935discusses amido transition metal compounds and catalyst systemsespecially for the production of isotactic polypropylene. Polymerizationcatalysts containing bidentate and tridentate ligands are furtherdiscussed in U.S. Pat. No. 5,506,184.

[0006] Traditional bulky ligand metallocene-type catalyst systemsproduce polymers that are in some situations more difficult to processinto film, for example using old extrusion equipment. One technique toimprove these polymers is to blend them with other polymers with theintent to create a blend having the desired properties that eachcomponent individually would have. While the two polymer blends tend tobe more processable, it is expensive and adds a cumbersome blending stepto the manufacturing/fabrication process.

[0007] Higher molecular weight confers desirable polymer mechanicalproperties and stable bubble formation in the production of films.However, this property also inhibits extrusion processing by increasingbackpressure in extruders, promotes melt fracture defects in theinflating bubble and potentially, promotes too high a degree oforientation in the finished film. The anionic, multidentate heteroatomcontaining catalyst systems tend to produce a very high molecular weightpolymer. To remedy this, one may form a secondary, minor component oflower molecular weight polymer to reduce extruder backpressure andinhibit melt fracture. Several industrial processes operate on thisprinciple using multiple reactor technology to produce a processablebimodal molecular weight distribution (MWD) high density polyethylene(HDPE) product. HIZEX™, a Mitsui Chemicals HDPE product, is consideredthe worldwide standard. HIZEX™ is produced in a costly two or morereactor process. In a multiple reactor process, each reactor produces asingle component of the final product.

[0008] Others in the art have tried to produce two polymers together atthe same time in the same reactor using two different catalysts. PCTpatent application WO 99/03899 discloses using a typical bulky ligandmetallocene-type catalyst and a conventional-type Ziegler-Natta catalystin the same reactor to produce a bimodal polyolefin. Using two differenttypes of catalysts, however, result in a polymer whose characteristicscannot be predicted from those of the polymers that each catalyst wouldproduce if utilized separately. This unpredictability occurs, forexample, from competition or other influence between the catalyst orcatalyst systems used.

[0009] Polyethylenes with a higher density and a higher molecular weightare valued in film applications requiring high stiffness, good toughnessand high throughput. Such polymers are also valued in pipe applicationsrequiring stiffness, toughness and long-term durability, andparticularly resistance to environmental stress cracking.

[0010] Thus, there is a desire for a combination of catalysts capable ofproducing processable polyethylene polymers in preferably a singlereactor having desirable combinations of processing, mechanical andoptical properties.

SUMMARY OF THE INVENTION

[0011] This invention provides for an improved catalyst compound, acatalyst system and for its use in a polymerizing process.

[0012] In one embodiment, the invention is directed to a catalyst systemincluding a Group 15 containing catalyst compound and a bulky ligandmetallocene-type catalyst compound, and a Lewis acid activator and toits use in the polymerization of olefin(s).

[0013] In another embodiment, the invention is directed to a catalystsystem of a Group 15 containing bidentate or tridentate ligatedtransition metal catalyst compound and a bulky ligand metallocene-typecatalyst compound and a Lewis acid aluminum containing activator and toits use in the polymerization of olefin(s).

[0014] In another embodiment, the invention is directed to a catalystsystem of a catalyst compound having a transition metal bound to atleast one leaving group and also bound to at least two Group 15 atoms,at least one of which is also bound to a Group 15 or 16 atom throughanother group, a bulky ligand metallocene-type catalyst compound and aLewis acid aluminum containing activator and to its use in thepolymerization of olefin(s).

[0015] In still another embodiment, the invention is directed to amethod for supporting a catalyst system of a multidentate ligatedtransition metal based catalyst compound, a bulky ligandmetallocene-type catalyst compound and a Lewis acid activator,preferably a Lewis acid aluminum containing activator on the same ordifferent supports; to the supported catalyst system itself; and totheir use in the polymerization of olefin(s), particularly in a slurryor gas phase process.

[0016] In another embodiment, the invention is directed to a process forpolymerizing olefin(s), particularly in a gas phase or slurry phaseprocess, utilizing any one of the catalyst systems or supports catalystsystems discussed above, more preferably in a continuous gas phasesingle reactor process producing a multimodal polymer.

BRIEF DESCRIPTION OF THE DRAWINGS

[0017]FIG. 1 is a gel permeation chromatogram representative of thepolymers of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0018] Introduction

[0019] It has been found that the Group 15 containing transition metalcatalyst compounds have a very high activity and typically produce in apolymerization process a polymer having a very high molecular weight.Bulky ligand metallocene-type catalysts typically have a high catalystproductivity and generally produce polymers having a lower molecularweight. It is also been found that using a Lewis acid aluminumcontaining activator results in a catalyst system that exhibitscommercially acceptable productivity with excellent operability. As aresult of this discovery it is now possible to provide for a mixedcatalyst system that produces in a polymerization process a multimodal,especially a bimodal, polymer having a high molecular weight and a lowmolecular weight component. It was surprising that the these twodifferent catalyst compounds activated by a Lewis acid containingactivator would perform together in this independent way, especially ina gas phase or slurry phase polymerization process, and in particularwhen the catalyst system is supported on a support material.

[0020] Group 15 Containing Metal Catalyst Compound and Catalyst Systems

[0021] In one embodiment, the metal based catalyst compounds of theinvention are Group 15 bidentate or tridentate ligated transition metalcompound having at least one substituted hydrocarbon group, thepreferred Group 15 elements are nitrogen and/or phosphorous, mostpreferably nitrogen, and the preferred leaving group is a substitutedalkyl group having greater than 6 carbon atoms, preferably the alkylsubstituted with an aryl group.

[0022] The Group 15 containing metal catalyst compounds of the inventiongenerally include a transition metal atom bound to at least onesubstituted hydrocarbon leaving group and also bound to at least twoGroup 15 atoms, at least one of which is also bound to a Group 15 or 16atom through another group.

[0023] In one preferred embodiment, at least one of the Group 15 atomsis also bound to a Group 15 or 16 atom through another group, which maybe a hydrocarbon group, preferably a hydrocarbon group having 1 to 20carbon atoms, a heteroatom containing group, preferably silicon,germanium, tin, lead, or phosphorus. In this embodiment, it is furtherpreferred that the Group 15 or 16 atom be bound to nothing or ahydrogen, a Group 14 atom containing group, a halogen, or a heteroatomcontaining group. Additionally in these embodiment, it is preferred thateach of the two Group 15 atoms are also bound to a cyclic group that mayoptionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

[0024] In an embodiment of the invention, the Group 15 containing metalcompound of the invention is represented by the formulae:

[0025] wherein M is a metal, preferably a transition metal, morepreferably a Group 4, 5 or 6 metal, even more preferably a Group 4metal, and most preferably hafnium or zirconium; each X is independentlya leaving group, preferably, an anionic leaving group, and morepreferably hydrogen, a hydrocarbyl group, a heteroatom (silyl, germylstannyl groups and the like), and most preferably an alkyl. In a mostpreferred embodiment, at least one X is a substituted hydrocarbon group,preferably a substituted alkyl group having more than 6 carbon atoms,more preferably an aryl substituted alkyl group and most preferably abenzyl group.

[0026] y is 0 or 1 (when y is 0 group L′ is absent);

[0027] n is the oxidation state of M, preferably +2, +3, +4 or +5 andmore preferably +4;

[0028] m is the formal charge of the YZL or the YZL′ ligand, preferably0, −1, −2 or −3, and more preferably −2;

[0029] L is a Group 15 or 16 element, preferably nitrogen;

[0030] L′ is a Group 15 or 16 element or Group 14 containing group,preferably carbon, silicon or germanium;

[0031] Y is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen;

[0032] Z is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen;

[0033] R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, or phosphorus, preferably a C₂ to C₂₀ alkyl, arylor arylalkyl group, more preferably a linear, branched or cyclic C₂ toC₂₀ alkyl group, most preferably a C₂ to C₆ hydrocarbon group;

[0034] R³ is absent or a hydrocarbon group, hydrogen, a halogen, aheteroatom containing group, preferably a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms, more preferably R³ is absent,hydrogen or an alkyl group, and most preferably hydrogen;

[0035] R⁴ and R⁵ are independently an alkyl group, an aryl group,substituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, a cyclic arylalkyl group, a substituted cyclic arylalkyl group ormultiple ring system, preferably having up to 20 carbon atoms, morepreferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀arylalkyl group, or a heteroatom containing group, for example PR₃,where R is an alkyl group;

[0036] R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵may be interconnected to each other;

[0037] R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent; and

[0038] R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, a heteroatom containing group.

[0039] By “formal charge of the YZL or YZL′ ligand”, it is meant thecharge of the entire ligand absent the metal and the leaving groups X.

[0040] By “R¹ and R² may also be interconnected” it is meant that R¹ andR² may be directly bound to each other or may be bound to each otherthrough other groups. By “R⁴ and R⁵ may also be interconnected” it ismeant that R⁴ and R⁵ may be directly bound to each other or may be boundto each other through other groups.

[0041] An alkyl group may be a linear, branched alkyl radicals, oralkenyl radicals, alkynyl radicals, cycloalkyl radicals or arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An arylalkyl group is defined to be a substitutedaryl group.

[0042] In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

[0043] wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀alkyl group, a halide, a heteroatom, a heteroatom containing groupcontaining up to 40 carbon atoms, preferably a C₁ to C₂₀ linear orbranched alkyl group, preferably a methyl, ethyl, propyl or butyl group,any two R groups may form a cyclic group and/or a heterocyclic group.The cyclic groups may be aromatic. In a preferred embodiment R⁹, R¹⁰ andR¹² are independently a methyl, ethyl, propyl or butyl group (includingall isomers), in a preferred embodiment R⁹, R¹⁰ and R¹² are methylgroups, and R⁸ and R¹¹ are hydrogen.

[0044] In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

[0045] In this embodiment, M is hafnium or zirconium; each of L, Y, andZ is nitrogen; each of R¹ and R² is a hydrocarbyl group, preferably—CH₂—CH₂—; R³ is hydrogen; and R⁶ and R⁷ are absent.

[0046] The Group 15 containing metal catalyst compounds of the inventionare prepared by methods known in the art, such as those disclosed in EP0 893 454 A1, U.S. Pat. No. 5,889,128 and the references cited in U.S.Pat. No. 5,889,128 which are all herein incorporated by reference. U.S.application Ser. No. 09/312,878, filed May 17, 1999, discloses a gas orslurry phase polymerization process using a supported bisamide catalyst,which is also incorporated herein by reference. A preferred directsynthesis of these compounds comprises reacting the neutral ligand, (seefor example YZL or YZL′ of Formula I or II) with MX_(n), n is theoxidation state of the metal, each X is an anionic group, such ashalide, in a non-coordinating or weakly coordinating solvent, such asether, toluene, xylene, benzene, methylene chloride, and/or hexane orother solvent having a boiling point above 60° C., at about 20° C. toabout 150° C. (preferably 20° C. to 100° C.), preferably for 24 hours ormore, then treating the mixture with an excess (such as four or moreequivalents) of an alkylating agent, such as methyl magnesium bromide inether. The magnesium salts are removed by filtration, and the metalcomplex isolated by standard techniques.

[0047] In one embodiment the Group 15 containing metal catalyst compoundis prepared by a method comprising reacting a neutral ligand, (see forexample YZL or YZL′ of formula 1 or 2) with a compound represented bythe formula MX_(n) (where n is the oxidation state of M, M is atransition metal, and each X is an anionic leaving group) in anon-coordinating or weakly coordinating solvent, at about 20° C. orabove, preferably at about 20° C. to about 100° C., then treating themixture with an excess of an alkylating agent, then recovering the metalcomplex. In a preferred embodiment the solvent has a boiling point above60° C., such as toluene, xylene, benzene, and/or hexane. In anotherembodiment the solvent comprises ether and/or methylene chloride, eitherbeing preferable.

[0048] Bulky Ligand Metallocene-Type Catalyst Compounds

[0049] Generally, bulky ligand metallocene-type catalyst compoundsinclude half and full sandwich compounds having one or more bulkyligands bonded to at least one metal atom. Typical bulky ligandmetallocene-type compounds are generally described as containing one ormore bulky ligand(s) and one or more leaving group(s) bonded to at leastone metal atom. In one preferred embodiment, at least one bulky ligandsis η-bonded to the metal atom, most preferably η⁵-bonded to the metalatom.

[0050] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

[0051] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention are represented by the formula:

L^(A)L^(B)MQ_(n)  (I)

[0052] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is a Group 4 transition metal,even more preferably M is zirconium, hafnium or titanium. The bulkyligands, L^(A) and L^(B), are open, acyclic or fused ring(s) or ringsystem(s) and are any ancillary ligand system, including unsubstitutedor substituted, cyclopentadienyl ligands or cyclopentadienyl-typeligands, heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (I) only one of either L^(A) or L^(B) is present.

[0053] Independently, each L^(A) and L_(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0054] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. For the purposes of this patent specification andappended claims the term “leaving group” is any ligand that can beabstracted from a bulky ligand metallocene-type catalyst compound toform a bulky ligand metallocene-type catalyst cation capable ofpolymerizing one or more olefin(s). In one embodiment, Q is amonoanionic labile ligand having a sigma-bond to M. Depending on theoxidation state of the metal, the value for n is 0, 1 or 2 such thatformula (I) above represents a neutral bulky ligand metallocene-typecatalyst compound.

[0055] Non-limiting examples of preferred Q ligands include hydrides,hydrocarbyls, silyls, germyls, scannyl's, dienes, alkylidenes andcarbenes. Most preferably the Q ligand is a hydrocarbyl radical havingfrom 1 to 20 carbon atoms or a hydride.

[0056] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention include those of formula (I) where LA and LBare bridged to each other by at least one bridging group, A, such thatthe formula is represented by

L^(A)AL^(B)MQ_(n)  (II)

[0057] These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (II) have two or morebridging groups A (EP 664 301 B1).

[0058] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those where the R substituents on the bulky ligands L^(A)and L^(B) of formulas (I) and (II) are substituted with the same ordifferent number of substituents on each of the bulky ligands. Inanother embodiment, the bulky ligands LA and LB of formulas (I) and (II)are different from each other.

[0059] Other bulky ligand metallocene-type catalyst compounds andcatalyst systems useful in the invention may include those described inU.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401,5,723,398, 5,753,578, 5,854,363, 5,856,547, 5,858,903, 5,859,158,5,900,517, 5,939,503 and 5,962,718 and PCT publications WO 93/08221, WO93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO98/46650, WO 99/02540 and WO 99/14221 and European publications EP-A-0578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839834, EP-B1-0 632 819, EP-B1-0 739 361, EP-B1-0 748 821 and EP-B1-0 757996, all of which are herein fully incorporated by reference.

[0060] In one embodiment, bulky ligand metallocene-type catalystscompounds useful in the invention include bridged heteroatom, mono-bulkyligand metallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all ofwhich are herein fully incorporated by reference.

[0061] In this embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(C)AJMQ_(n)  (HI)

[0062] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillaryligand; and A is a bridging group; Q is a univalent anionic ligand; andn is the integer 0, 1 or 2. In formula (III) above, L^(C), A and J forma fused ring system. In an embodiment, L^(C) of formula (III) is asdefined above for L^(A), A, M and Q of formula (III) are as definedabove in formula (I).

[0063] In formula (III) J is a heteroatom containing ligand in which Jis an element with a coordination number of three from Group 15 or anelement with a coordination number of two from Group 16 of the PeriodicTable of Elements. Preferably J contains a nitrogen, phosphorus, oxygenor sulfur atom with nitrogen being most preferred.

[0064] In another embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B 1-0 735057, all of which are herein fully incorporated by reference.

[0065] In an embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(D)MQ₂(YZ)X_(n)  (IV)

[0066] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; L^(D) is a bulky ligand that is bonded to M; each Q isindependently bonded to M and Q₂(YZ) forms a unicharged polydentateligand; A or Q is a univalent anionic ligand also bonded to M; X is aunivalent anionic group when n is 2 or X is a divalent anionic groupwhen n is 1; n is 1 or 2.

[0067] In formula (IV), L and M are as defined above for formula (I). Qis as defined above for formula (I), preferably Q is selected from thegroup consisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0068] In another embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095(dicarbamoyl metal complexes) and EP-A1-0 874 005 and U.S. Pat. Nos.5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and5,856,258 all of which are herein incorporated by reference.

[0069] In another embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

[0070] In one embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (V)

[0071] where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X, Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

[0072] It is also contemplated that in one embodiment, the bulky ligandmetallocene-type catalysts of the invention described above includetheir structural or optical or enantiomeric isomers (meso and racemicisomers, for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

[0073] Activator and Activation Methods

[0074] The above described Group 15 containing metal catalyst compoundand bulky ligand metallocene-type catalysts compounds are typicallyactivated in various ways to yield catalyst compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s).

[0075] The preferred activator is a Lewis acid compound, more preferablyan aluminum based Lewis acid compound, and most preferably a neutral,aluminum based Lewis acid compound having at least one, preferably two,halogenated aryl ligands and one or two additional monoanionic ligandsnot including halogenated aryl ligands.

[0076] The Lewis acid compounds of the invention include those olefincatalyst activator Lewis acids based on aluminum and having at least onebulky, electron-withdrawing ancillary ligand such as the halogenatedaryl ligands of tris(perfluorophenyl)borane ortris(perfluoronaphthyl)borane. These bulky ancillary ligands are thosesufficient to allow the Lewis acids to function as electronicallystabilizing, compatible non-coordinating anions. Stable ionic complexesare achieved when the anions will not be a suitable ligand donor to thestrongly Lewis acidic cationic Group 15 containing transition metalcations used in insertion polymerization, i.e., inhibit ligand transferthat would neutralize the cations and render them inactive forpolymerization.

[0077] The Lewis acids fitting this description can be described by thefollowing formula:

R_(n)Al(ArHal)_(3-n),  (V)

[0078] where R is a monoanionic ligand and ArHal is a halogenated C₆aromatic or higher carbon number polycyclic aromatic hydrocarbon oraromatic ring assembly in which two or more rings (or fused ringsystems) are joined directly to one another or together, and n=1 to 2,preferably n=1.

[0079] In one embodiment, at least one (ArHal) is a halogenated C₉aromatic or higher, preferably a fluorinated naphtyl. Suitablenon-limiting R ligands include: substituted or unsubstituted C₁ to C₃₀hydrocarbyl aliphatic or aromatic groups, substituted meaning that atleast one hydrogen on a carbon atom is replaced with a hydrocarbyl,halide, halocarbyl, hydrocarbyl or halocarbyl substitutedorganometalloid, dialkylamido, alkoxy, siloxy, aryloxy, alkysulfido,arylsulfido, alkylphosphido, alkylphosphido or other anionicsubstituent; fluoride; bulky alkoxides, where bulky refers to C₄ andhigher number hydrocarbyl groups, e.g., up to about C₂₀, such astert-butoxide and 2,6-dimethyl-phenoxide, and2,6-di(tert-butyl)phenoxide; —SR; —NR₂, and —PR₂, where each R isindependently a substituted or unsubstituted hydrocarbyl as definedabove; and, C₁ to C₃₀ hydrocarbyl substituted organometalloid, such astrimethylsilyl.

[0080] Examples of ArHal include the phenyl, napthyl and anthracenylradicals of U.S. Pat. No. 5,198,401 and the biphenyl radicals of WO97/29845 when halogenated. The use of the terms halogenated orhalogenation means for the purposes of this application that at leastone third of hydrogen atoms on carbon atoms of the aryl-substitutedaromatic ligands are replaced by halogen atoms, and more preferred thatthe aromatic ligands be perhalogenated. Fluorine is the most preferredhalogen.

[0081] Other activators or methods of activation are contemplated foruse with the aluminum based Lewis acid activators. For example otheractivators include: alumoxane, modified alumoxane, tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions, trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, tris (2,2′,2″-nona-fluorobiphenyl) fluoroaluminate,perchlorates, periodates, iodates and hydrates,(2,2′-bisphenyl-ditrimethylsilicate).4THF and organo-boron-aluminumcompound, silylium salts anddioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)-benzimidazolide.

[0082] It is further contemplated by the invention that other catalystsincluding bulky ligand metallocene-type catalyst compounds and/orconventional-type catalyst compounds can be combined with the Group 15containing metal catalyst compounds of this invention. It is alsocontemplated that in addition to the Lewis acid aluminum containingactivator that other activators such as alumoxane, modified alumoxane,organoaluminum compounds such as trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike, or a combination thereof, may be used.

[0083] It is further contemplated by the invention that aconventional-type catalyst compound can be combined with the Group 15containing metal catalyst compounds and the bulky ligandmetallocene-type catalyst compounds of this invention.

[0084] Supports, Carriers and General Supporting Techniques

[0085] The above described catalyst systems of a Group 15 containingmetal catalyst compound, a bulky ligand metallocene-type catalystcompound and a Lewis acid aluminum containing activator may be combinedwith one or more support materials or carriers using one of the supportmethods well known in the art or as described below. For example, in amost preferred embodiment, a Group 15 containing metal catalystcompound, a bulky ligand metallocene-type catalyst compound and Lewisacid activator is in a supported form, for example deposited on,contacted with, vaporized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, a support or carrier.

[0086] The R group in formula (V) above, or ligand, may also be acovalently bonded to a support material, preferably a metal/metalloidoxide or polymeric support. Lewis base-containing support materials orsubstrates will react with the Lewis acid activators to form a supportbonded Lewis acid compound, a supported activator, where one R group ofR_(n)Al(ArHal)_(3-n) is covalently bonded to the support material. Forexample, where the support material is silica, the Lewis base hydroxylgroups of the silica is where this method of bonding at one of thealuminum coordination sites occurs.

[0087] In a preferred embodiment, the support material is a metal ormetalloid oxide, preferably having surface hydroxyl groups exhibiting apK_(a) equal to or less than that observed for amorphous silica, i.e.,pK_(a) less than or equal to about 11.

[0088] While not wishing to be bound to any particular theory, it isbelieved that the covalently bound anionic activator, the Lewis acid, isbelieved to form initially a dative complex with a silanol group, forexample of silica (which acts as a Lewis base), thus forming a formallydipolar (zwitterionic) Bronsted acid structure bound to themetal/metalloid of the metal oxide support. Thereafter, the proton ofthe Bronsted acid appears to protonate an R-group of the Lewis acid,abstracting it, at which time the Lewis acid becomes covalently bondedto the oxygen atom. The replacement R group of the Lewis acid thenbecomes R′—O—, where R′ is a suitable support material or substrate, forexample, silica or hydroxyl group-containing polymeric support. Anysupport material that contain surface hydroxyl groups are suitable foruse in this particular supporting method. Other support material includeglass beads.

[0089] In one embodiment where the support material is a metal oxidecomposition, these compositions may additionally contain oxides of othermetals, such as those of Al, K, Mg, Na, Si, Ti and Zr and shouldpreferably be treated by thermal and/or chemical means to remove waterand free oxygen. Typically such treatment is in a vacuum in a heatedoven, in a heated fluidized bed or with dehydrating agents such asorgano silanes, siloxanes, alkyl aluminum compounds, etc. The level oftreatment should be such that as much retained moisture and oxygen as ispossible is removed, but that a chemically significant amount ofhydroxyl functionality is retained. Thus calcining at up to 800° C. ormore up to a point prior to decomposition of the support material, forseveral hours is permissible, and if higher loading of supported anionicactivator is desired, lower calcining temperatures for lesser times willbe suitable. Where the metal oxide is silica, loadings to achieve fromless than 0.1 mmol to 3.0 mmol activator/g SiO₂ are typically suitableand can be achieved, for example, by varying the temperature ofcalcining from 200 to 800+° C. See Zhuralev, et al, Langmuir 1987, Vol.3, 316 where correlation between calcining temperature and times andhydroxyl contents of silica's of varying surface areas is described.

[0090] The tailoring of hydroxyl groups available as attachment sitescan also be accomplished by the pre-treatment, prior to addition of theLewis acid, with a less than stoichiometric amount of the chemicaldehydrating agents. Preferably those used will be used sparingly andwill be those having a single ligand reactive with the silanol groups(e.g., (CH₃)₃SiCl), or otherwise hydrolyzable, so as to minimizeinterference with the reaction of the transition metal catalystcompounds with the bound activator. If calcining temperatures below 400°C. are employed, difunctional coupling agents (e.g., (CH₃)₂SiCl₂) may beemployed to cap hydrogen bonded pairs of silanol groups which arepresent under the less severe calcining conditions. See for example,“Investigation of Quantitative SiOH Determination by the SilaneTreatment of Disperse Silica”, Gorski, et al, Journ. of Colloid andInterface Science, Vol. 126, No. 2, December 1988, for discussion of theeffect of silane coupling agents for silica polymeric fillers that willalso be effective for modification of silanol groups on the catalystsupports of this invention. Similarly, use of the Lewis acid in excessof the stoichiometric amount needed for reaction with the transitionmetal compounds will serve to neutralize excess silanol groups withoutsignificant detrimental effect for catalyst preparation or subsequentpolymerization.

[0091] Polymeric supports are preferablyhydroxyl-functional-group-containing polymeric substrates, butfunctional groups may be any of the primary alkyl amines, secondaryalkyl amines, and others, where the groups are structurally incorporatedin a polymeric chain and capable of a acid-base reaction with the Lewisacid such that a ligand filling one coordination site of the aluminum isprotonated and replaced by the polymer incorporated functionality. See,for example, the functional group containing polymers of U.S. Pat. No.5,288,677, which is herein incorporated by reference.

[0092] Other supports include silica, alumina, silica-alumina, magnesia,titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate,zeolites, talc, clays, silica-chromium, silica-alumina, silica-titania,porous acrylic polymers.

[0093] In one embodiment, the support material or carrier, mostpreferably an inorganic oxide has a surface area in the range of fromabout 10 to about 100 m²/g, pore volume in the range of from about 0.1to about 4.0 cc/g and average particle size in the range of from about 5to about 500 μm. More preferably, the surface area of the carrier is inthe range of from about 50 to about 500 m²/g, pore volume of from about0.5 to about 3.5 cc/g and average particle size of from about 10 toabout 200 μm. Most preferably the surface area of the carrier is in therange is from about 100 to about 400 m²/g, pore volume from about 0.8 toabout 5.0 cc/g and average particle size is from about 5 to about 100μm. The average pore size of the carrier of the invention typically haspore size in the range of from 10 to 1000 Å, preferably 50 to about 500Å, and most preferably 75 to about 450 Å.

[0094] There are various other methods in the art for supporting apolymerization catalyst compound or catalyst system of the invention.

[0095] In a preferred embodiment, the invention provides for a Group 15containing metal catalyst compound, a bulky ligand metallocene-typecatalyst compound, and the Lewis acid aluminum activator includes asurface modifier that is used in the preparation of the supportedcatalyst system as described in PCT publication WO 96/11960, which isherein fully incorporated by reference. The catalyst systems of theinvention can be prepared in the presence of an olefin, for examplehexene-1.

[0096] In a preferred embodiment, the mixed catalyst system can becombined with a carboxylic acid salt of a metal ester, for examplealuminum carboxylates such as aluminum mono, di- and tri-stearates,aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S.application Ser. No. 09/113,216, filed Jul. 10, 1998.

[0097] A preferred method for producing a supported Group 15 containingmetal catalyst, a bulky ligand metallocene-type catalyst and a Lewisacid aluminum activator catalyst system is described below and isdescribed in U.S. application Ser. Nos. 265,533, filed Jun. 24, 1994 and265,532, filed Jun. 24, 1994 and PCT publications WO 96/00245 and WO96/00243 both published Jan. 4, 1996, all of which are herein fullyincorporated by reference. In this preferred method, the Group 15containing metal catalyst compound and/or separately the bulky ligandmetallocene-type catalyst compound is slurried in a liquid to form asolution and a separate solution is formed containing a Lewis acidactivator and a liquid. The liquid may be any compatible solvent orother liquid capable of forming a solution or the like with the Group 15containing metal catalyst compounds and or bulky ligand metallocene-typecatalyst compounds and/or Lewis acid activators. In the most preferredembodiment the liquid is a cyclic aliphatic or aromatic hydrocarbon,most preferably toluene. The Group 15 containing metal catalystcompounds and/or the bulky ligand metallocene-type catalyst compoundsand Lewis acid activator solutions are mixed together and added to aporous support such that the total volume of Group 15 containing metalcatalyst compound solution and/or a bulky ligand metallocene-typecatalyst compound and the Lewis acid activator solution or the Group 15containing metal catalyst compound solution and Lewis acid activatorsolution or the bulky ligand metallocene-type catalyst compound solutionor the combined catalyst compound solutions is less than four times thepore volume of the porous support, more preferably less than threetimes, even more preferably less than two times; preferred ranges beingfrom 1.1 times to 3.5 times range and most preferably in the 1.2 to 3times range.

[0098] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density ofFluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0099] In another embodiment of the invention, a Group 15 containingmetal catalyst compound and a Lewis acid aluminum containing activatoris supported on one support material and the bulky ligandmetallocene-type catalyst compound and the Lewis acid aluminumcontaining activators is supported on a second support material, and thetwo are introduced into the reactor simultaneously, separately, orcombined. In this embodiment, it would be preferably that the supportmaterials be the same. In an alternative embodiment, in only one of theseparately supported systems, the bulky ligand metallocene-type catalystcompound or the Group 15 containing metal catalyst compound is activatedwith alumoxane or the like replacing the Lewis acid aluminum containingactivator.

[0100] The mole ratio of the metal of the activator component to themetal component of the Group 15 containing metal catalyst compound ispreferably in the range of between 0.3:1 to 3:1.

[0101] In one embodiment of the invention, olefin(s), preferably C₂ toC₃₀ olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of the catalystsystem of the invention prior to the main polymerization. Theprepolymerization can be carried out batchwise or continuously in gas,solution or slurry phase including at elevated pressures. Theprepolymerization can take place with any olefin monomer or combinationand/or in the presence of any molecular weight controlling agent such ashydrogen. For examples of prepolymerization procedures, see U.S. Pat.Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578and European publication EP-B-0279 863 and PCT Publication WO 97/44371all of which are herein fully incorporated by reference.

[0102] Polymerization Process

[0103] The catalyst systems, supported catalyst systems of the inventiondescribed above are suitable for use in any prepolymerization and/orpolymerization process over a wide range of temperatures and pressures.The temperatures may be in the range of from −60° C. to about 280° C.,preferably from 50° C. to about 200° C., and the pressures employed maybe in the range from 1 atmosphere to about 500 atmospheres or higher.

[0104] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene.

[0105] In one embodiment, the process of this invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the polymerizationof two or more olefin monomers of ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[0106] Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbomene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

[0107] In the most preferred embodiment of the process of the invention,a copolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

[0108] In another embodiment of the process of the invention, ethyleneor propylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

[0109] In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms.

[0110] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0111] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0112] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about 115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0113] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

[0114] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0115] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0116] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

[0117] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0118] Examples of solution processes are described in U.S. Patent Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525, whichare fully incorporated herein by reference

[0119] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the presence ofmixed catalyst system of the -invention and in the absence of oressentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. No.5,712,352 and 5,763,543, which are herein fully incorporated byreference.

[0120] In an embodiment, the method of the invention provides forinjecting an unsupported mixed catalyst system into a reactor,particularly a gas phase reactor. In one embodiment the polymerizationcatalysts of the invention are used in the unsupported form, preferablyin a liquid form such as described in U.S. Pat. Nos. 5,317,036 and5,693,727 and European publication EP-A-0 593 083, all of which areherein incorporated by reference. The polymerization catalyst orcatalyst(s) in liquid form can be fed with an activator together orseparately to a reactor using the injection methods described in PCTpublication WO 97/46599, which is fully incorporated herein byreference.

[0121] The hydrogen concentration in the reactor is about 100 to 5000ppm, preferably 200 to 2000 ppm, more preferably 250 to 1900 ppm, morepreferably 300 to 1800 ppm, and more preferably 350 to 1700 ppm, morepreferably 400 to 1600 ppm, more preferably 500 to 1500 ppm, morepreferably 500 to 1400 ppm, more preferably 500 to 1200 ppm, morepreferably 600 to 1200 ppm, preferably 700 to 1100 ppm, and morepreferably 800 to 1000 ppm. The hydrogen concentration in the reactorbeing inversely proportional to the polymer's weight average molecularweight (Mw).

[0122] Polymer Products

[0123] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers. Preferably the new polymers includepolyethylene, and even more preferably include bimodal polyethyleneproduced in a single reactor. In addition to bimodal polymers, it is notbeyond the scope of the present application to produce a unimodal ormulti-modal polymer.

[0124] The polyolefins, particularly polyethylenes, produced by thepresent invention, have a density of 0.89 to 0.97g/cm³. Preferably,polyethylenes having a density of 0.910 to 0.965g/cm³, more preferably0.915 to 0.960 g/cm³, and even more preferably 0.920 to 0.955 g/cm³ canbe produced. In some embodiments, a density of 0.915 to 0.940 g/cm³would be preferred, in other embodiments densities of 0.930 to 0.970g/cm³ are preferred. Density is measured in accordance with ASTM-D-1238.

[0125] The polymers produced by the process of the invention typicallyhave a molecular weight distribution, a weight average molecular weightto number average molecular weight (M_(w)/M_(n)) of greater than 5,particularly greater than 10.

[0126] Also, the polymers of the invention typically have a narrowcomposition distribution as measured by Composition Distribution BreadthIndex (CDBI). Further details of determining the CDBI of a copolymer areknown to those skilled in the art. See, for example, PCT PatentApplication WO 93/03093, published Feb. 18, 1993, which is fullyincorporated herein by reference.

[0127] In another embodiment, polymers produced using a catalyst systemof the invention have a CDBI less than 50%, more preferably less than40%, and most preferably less than 30%.

[0128] In a preferred embodiment, the polyolefin recovered typically hasa melt index 12 (as measured by ASTM D-1238, Condition E at 190° C. ) ofabout 0.01 to 1000 dg/min or less. In a preferred embodiment, thepolyolefin is ethylene homopolymer or copolymer. In a preferredembodiment for certain applications, such as films, pipes, moldedarticles and the like, a melt index of 10 dg/min or less is preferred.For some films and molded articles, a melt index of 1 dg/min or less ispreferred. Polyethylene having a 12 between 0.01 and 10 min ispreferred.

[0129] In a preferred embodiment the polymer produced herein has an I₂₁(as measured by ASTM-D-1238-F, at 190° C.) of 0.1 to 100 dg/min,preferably 0.5 dg/min to 50 dg/min, more preferably 2 dg/min to 20dg/min (especially for pipe applications), and most preferably for filmapplications from 5 dg/min to 10 dg/min.

[0130] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 80, more preferably greater than 90, even morepreferably greater that 100, still even more preferably greater than 110and most preferably greater than 120.

[0131] The Group 15 containing metal compound, when used alone, producesa high weight average molecular weight Mw polymer such as for exampleabove 100,000, preferably above 150,000, preferably above 200,000,preferably above 250,000, more preferably above 300,000).

[0132] The bulky ligand metallocene-type catalyst compound, when usealone produces a low weight average molecular weight polymer such as forexample below 100,000, preferably below 80,000, more preferably below60,000, still more preferably below 50,000, still even more preferablybelow 40,000, and most preferably less than 30,000 and greater than5,000.

[0133] In another embodiment the polymer has one or more of thefollowing properties in addition to a combination of those above:

[0134] (a) M_(w)/M_(n) of between 15 and 80, preferably between 20 and60, preferably between 20 and 40. Molecular weight (M_(w) and M_(n)) aremeasured as described below in the examples section;

[0135] (b) a density (as measured by ASTM 2839) of 0.94 to 0.970 g/cm³;preferably 0.945 to 0.965 g/cm³; preferably 0.945 g/cm³ to 0.960 g/cm³;

[0136] (c) a residual metal content of 5.0 ppm transition metal or less,preferably 2.0 ppm transition metal or less, preferably 1.8 ppmtransition metal or less, preferably 1.6 ppm transition metal or less,preferably 1.5 ppm transition metal or less, preferably 2.0 ppm or lessof Group 4 metal, preferably 1.8 ppm or less of Group 4 metal,preferably 1.6 ppm or less of Group 4 metal, preferably 1.5 ppm or lessof Group 4 metal (as measured by Inductively Coupled Plasma EmissionSpectroscopy (ICPES) run against commercially available standards, wherethe sample is heated so as to fully decompose all organics and thesolvent comprises nitric acid and, if any support is present, anotheracid to dissolve any support (such as hydrofluoric acid to dissolvesilica supports) is present; and/or

[0137] (d) 35 weight percent or more high weight average molecularweight component, as measured by size-exclusion chromatography,preferably 40% or more. In a particularly preferred embodiment thehigher molecular weight fraction is present at between 35 and 70 weight%, more preferably between 40 and 60 weight %.

[0138] In one preferred embodiment the catalyst composition describedabove is used to make a polyethylene having a density of between 0.94and 0.970 g/cm³ (as measured by ASTM D 2839) and an 12 of 0.5 or lessg/10 min or less. In another embodiment the catalyst compositiondescribed above is used to make a polyethylene having an I₂₁ of lessthan 10 and a density of between about 0.940 and 0.950g/cm³ or an I₂₁ ofless than 20 and a density of about 0.945g/cm³ or less.

[0139] In another embodiment, the polymers of the invention, includingthose described above, have an ash content less than 100 ppm, morepreferably less than 75 ppm, and even more preferably less than 50 ppmis produced. In another embodiment, the ash contains negligibly smalllevels, trace amounts, of titanium as measured by Inductively CoupledPlasma/Atomic Emission Spectroscopy (ICPAES) as is well known in theart.

[0140] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes, elastomers, plastomers, high pressurelow density polyethylene, high density polyethylenes, polypropylenes andthe like.

[0141] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, pipe,geomembranes, and pond liners. Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollowarticles, rigid food containers and toys, etc.

EXAMPLES

[0142] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

[0143] The following examples below use the bulky ligandmetallocene-type catalyst compound(dimethylsilylbis(3-n-propylcyclopentadienyl)zirconium dichloride(DMSP-Cl₂)), which was obtained from Boulder Scientific, Meade, Colo.Synthesis of Al(C6F5)3.toluene was prepared in accordance with method ofdescribed in EP 0 694 548 A1, which is fully incorporated by reference.

Example 1

[0144] Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH2]₂NH Ligand

[0145] A 2 L one-armed Schlenk flask was charged with a magnetic stirbar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51g, 0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemicBINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol),and toluene (800 mL) under dry, oxygen-free nitrogen. The reactionmixture was stirred and heated to 100° C. After 18 h the reaction wascomplete, as judged by proton NMR spectroscopy. All remainingmanipulations can be performed in air. All solvent was removed undervacuum and the residues dissolved in diethyl ether (1 L). The ether waswashed with water (3 times 250 mL) followed by saturated aqueous NaCl(180 g in 500 mL) and dried over magnesium sulfate (30 g). Removal ofthe ether in vacuo yielded a red oil which was dried at 70° C. for 12 hunder vacuum (yield: 71.10 g, 92%). ¹H NMR (C₆D₆) δ 6.83 (s, 4), 3.39(br s, 2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (brs, 1).

Example 2

[0146] Preparation of {[(2,4,6-Me₃C₆H₂)NHCH₂]₂NH}Hf(CH₂Ph)₂ (Hf—HN₃)

[0147] A 250 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl hafnium (4.063 g, 7.482 mmol), and 150 mL of toluene underdry, oxygen-free nitrogen. Solid triamine ligand above (2.545 g, 7.495mmol) was added with stirring over 1 minute (the desired compoundprecipitates). The volume of the slurry was reduced to 30 mL and 120 mLof pentane added with stirring. The solid pale yellow product wascollected by filtration and dried under vacuum (4.562 g, 87% yield). ¹HNMR (C₆D₆) δ 7.21-6.79 (m, 12), 6.16 (d, 2), 3.39 (m, 2), 3.14 (m, 2),2.65 (s, 6), 2.40 (s, 6), 2.35 (m, 2), 2.23 (m, 2), 2.19 (s, 6) 1.60 (s,2), 1.26 (s, 2), NH obscured.

Example 3

[0148] Preparation ofDimethylsilylbis(3-n-propylcyclopentadienyl)zirconium Dimethyl(DMSP-Me₂)

[0149] A 250 mL round bottom flask was charged with a magnetic stir bar,5.990 g of DMSP-C12 (13.84 mmol) and 125 mL of diethyl ether. Thesolution was cooled to −30° C. and 20.3 mL of MeLi (1.4 M in ether,28.42 mmol) added dropwise with stirring over 5 minutes. The mixture waswarmed to room temperature and stirred for 2 hours. The ether wasremoved under vacuum and the residues extracted with 50 mL toluene. Thetoluene mixture was filtered through Celite to remove LiCl and thetoluene removed under vacuum. The oily residues were dissolved inpentane, filtered through Celite, and the solvent removed to give aclear yellow oil. The oil is a 1:1 mixture of rac and meso. ¹H NMR(C₆D₆) δ 6.49 (m, 4), 5.48 (m, 2), 5.39 (m, 2), 5.25 (m, 2), 5.20 (m,2), 2.59 (m, CH₂, 8), 1.62 (m, CH₂, 8), 0.96 (m, CH₃, 12), 0.20 (s,SiMe, 3), 0.18 (s, SiMe, 6), 0.16 (s, SiMe, 3), −0.08 (s, ZrMe, 3),−0.17 (s, ZrMe, 6), −0.23 (s, ZrMe, 3).

Example 4

[0150] Preparation of Silica Bound Aluminum (—Si—O—Al(C₆F₅)₂)

[0151] 11.50 g of silica (Davison 948, calcined at 600° C. availablefrom W. R. Grace, Davison Division, Baltimore, Md.) was slurried in 300mL of toluene in a 500 mL round bottom flask and solid Al(C₆F₅)₃.toluene(5.706 g, 24.90 mmol) added. The mixture was heated to 85° C. for 1 hourthen left to cool overnight (20 hours). The silica bound aluminum wasisolated by filtration and dried for 6 hours under vacuum (yield, 13.81g).

Example 5

[0152] Preparation of Catalyst A

[0153] To 1.000 g of silica bound aluminum (from Example 4) in 20 mL oftoluene was added Hf-HN3 (0.056 g, 0.080 mmol) (from Example 2) in 5 mLof toluene. The mixture was stirred for 30 minutes. The silica turnedorange-red from colorless. The silica was isolated by filtration anddried under vacuum for 6 hours (yield, 1.041 g). The final transitionmetal loading was 76 μmol/g.

Example 6

[0154] Preparation of Catalyst B

[0155] To 1.000 g of silica bound aluminum (from Example 4) in 20 mL oftoluene was added DMSP-Me₂ (0.031 g, 0.079 mmol) (from Example 3) in 5mL of toluene. The mixture was stirred for 30 minutes. The silica turnedorange-red from colorless. The silica was isolated by filtration anddried under vacuum for 6 hours (yield, 1.059 g). The final transitionmetal loading was 76 μmol/g.

Example 7

[0156] Preparation of Catalyst C (Mixture)

[0157] To 2.000 g of silica bound aluminum (from Example 4) in 40 mL oftoluene was added Hf—HN3 (0.098 g, 0.140 mmol) (from Example 2) andDMSP-Me2 (0.008 g, 0.20 mmol) (from Example 3). The mixture was stirredfor 30 minutes. The silica turned orange-red from colorless. The silicawas isolated by filtration and dried under vacuum for 6 hours (yield,2.065 g). The final transition metal loading was 76 μmol/g.

Example 8

[0158] Slurry-Phase Ethylene Polymerization with Catalyst A

[0159] Polymerization was performed in the slurry-phase in a 1-literautoclave reactor equipped with a mechanical stirrer, an external waterjacket for temperature control, a septum inlet, a vent line, and aregulated supply of dry nitrogen and ethylene. The reactor was dried anddegassed at 160° C. Triisobutyl aluminum (100 μL) was added as ascavenger using a gas tight syringe followed by isobutane (400 mL)diluent. The reactor was heated to 85° C. 0.025 g of finished Catalyst Awas added with ethylene pressure and the reactor was pressurized with124 psi (975 kPa) of ethylene. The polymerization was continued for 40minutes while maintaining the reactor at 85° C. and 124 psi (975 kPa) byconstant ethylene flow. The reaction was stopped by rapid cooling andvented. 9.2 g of polyethylene was obtained (Fl=no flow, activity=879 gpolyethylene/mmol catalyst.atm.h).

Example 9

[0160] Slurry-Phase Ethylene Polymerization with Catalyst B

[0161] Polymerization was performed in the slurry-phase in a 1-literautoclave reactor equipped with a mechanical stirrer, an external waterjacket for temperature control, a septum inlet, a vent line, and aregulated supply of dry nitrogen and ethylene. The reactor was dried anddegassed at 160° C. Triisobutyl aluminum (100 μL) was added as ascavenger using a gas tight syringe followed by isobutane (400 mL)diluent. The reactor was heated to 85° C. 0.025 g of finished Catalyst Bwas added with ethylene pressure and the reactor was pressurized with122 psi (959 kPa) of ethylene. The polymerization was continued for 40minutes while maintaining the reactor at 85° C. and 122 psi (959 kPa) byconstant ethylene flow. The reaction was stopped by rapid cooling andvented. 74.7 g of polyethylene was obtained (I=193, activity=7250 gpolyethylene/mmol catalyst.atm.h).

Example 10

[0162] Slurry-Phase Ethylene Polymerization with Catalyst C

[0163] Polymerization was performed in the slurry-phase in a 1-literautoclave reactor equipped with a mechanical stirrer, an external waterjacket for temperature control, a septum inlet, a vent line, and aregulated supply of dry nitrogen and ethylene. The reactor was dried anddegassed at 160° C. Triisobutyl aluminum (100 μL) was added as ascavenger using a gas tight syringe followed by isobutane (400 mL)diluent. The reactor was heated to 85° C. 0.025 g of finished Catalyst Cwas added with ethylene pressure and the reactor was pressurized with123 psi (967 kPa) of ethylene. The polymerization was continued for 40minutes while maintaining the reactor at 85° C. and 123 psi (967 kPa) byconstant ethylene flow. The reaction was stopped by rapid cooling andvented. 17.2 g of polyethylene was obtained (Fl=10.9, activity=1656 gpolyethylene/mmol catalyst.atm.h).

[0164] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that twoor more supported Group 15 containing catalyst compositions of theinvention can be used with an unsupported bulky ligand metallocene-typecatalyst compound. For this reason, then, reference should be madesolely to the appended claims for purposes of determining the true scopeof the present invention.

We claim:
 1. A supported catalyst system comprising: a Group 15containing metal catalyst compound, a bulky ligand metallocene-typecatalyst compound, a Lewis acid aluminum containing activator and acarrier, wherein the Lewis acid aluminum containing activator isrepresented by the following formula: R_(n)Al(ArHal)_(3-n), wherein R isa monoanionic ligand; ArHal is a halogenated C₆ aromatic or highercarbon number polycyclic aromatic hydrocarbon or aromatic ring assemblyin which two or more rings are joined directly to one another ortogether; and n=1 or
 2. 2. The supported catalyst system of claim 1wherein the Group 15 containing metal catalyst compound is a Group 15containing bidentate or tridentate ligated metal catalyst compound. 3.The supported catalyst system of claim 1 wherein the Group 15 containingmetal catalyst compound and the bulky ligand metallocene-type catalystcompound are contacted with the Lewis acid aluminum containing activatorto form a reaction product that is then contacted with the carrier. 4.The supported catalyst system of claim 1 wherein the carrier and theLewis acid aluminum containing activator are combined to form a supportbound, neutral Lewis acid aluminum containing activator having at leastone ligand covalently bound to a support material.
 5. The supportedcatalyst system of claim 4 wherein the support material is a polymericsupport or a metal/metalloid oxide support.
 7. The supported catalystsystem of claim 4 wherein the at least one ligand is a heteroatom thatis covalently bound to the support material.
 8. The supported catalystsystem of claim 4 wherein the Lewis acid aluminum containing activatorfurther comprises at least two halogenated aryl ligands.
 9. Thesupported catalyst system of claim 1 wherein the supported catalystsystem further comprises alumoxane.
 10. A method of making a supportedcatalyst system, method comprising the steps of: (a) combining a Group15 metal containing catalyst compound and a bulky ligandmetallocene-type catalyst compound; (b) combining a support materialwith a Lewis acid aluminum containing activator represented by theformula: R_(n)Al(ArHal)_(3-n), wherein R is a monoanionic ligand; ArHalis a halogenated C₆ aromatic or higher carbon number polycyclic aromatichydrocarbon or aromatic ring assembly in which two or more rings arejoined directly to one another or together; and n=1 or 2; and (c)combining (a) and (b).
 11. The method of claim 10 wherein in step (b)the Lewis acid aluminum containing activator is covalently bound to thesupport material.